Control of plant pathogenic fungi with 1-halo-2-aryloxy-vinyl-(2)phosphates

ABSTRACT

1. A METHOD FOR CONTROLLING PLANT PATHOGENIC FUNGI WHICH COMPRISES APPLYING THEREOT A FUNGICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA   R1-O-P(=O)(-O-R2)-O-C(=CH-HAL)-O-R3   IN WHICH HAL REPRESENTS CHLORINE OR BROMINE; EACH OF R1 AND R2 REPRESENTS ALKYL OF FROM 1 TO 4 CARBON ATOMS; AND R3 REPRESENTS PHENYL, NAPHTHYL OR PHENYL SUBSTITUTED BY FROM 1 TO 5 SUBSTITUENTS SELECTED FROM THE GROUP CONSISTING OF CHLORINE, BROMINE, IODINE, ALKYL OF FROM 1 TO 4 CARBON ATOMS, ALKOXY OF FROM 1 TO 4 CARBON ATOMS, ALKYLTHIO OF FROM 1 TO 4 CARBON ATOMS, NITRO, TRIFLUOROMETHYL, CYANO, THE GROUP -COO-ALKYL IN WHICH THE ALKYL GROUP HAS FROM 1 TO 4 CARBON ATOMS AND THE GROUP -CO-ALKYL IN WHICH THE ALKYL HAS FROM 1 TO 4 CARBON ATOMS.

United States Patent M 3,840,660 CONTROL OF PLANT PATHOGENIC FUNGI WITH 1-HALO-2-ARYLOXY-VINYL-(2) PHOSPHATES Henry Martin and Jozef Drabek, Basel, Switzerland, assignors to 'Ciba-Geigy AG, Basel, Switzerland No Drawing. Original application Aug. 17, 1970, Ser. No. 64,648, now Patent No. 3,732,343. Divided and this application Feb. 14, 1973, Ser. No. 332,469 Claims priority, application Switzerland, Aug. 18, 1969, 12,553; Sept. 25, 1969, 14,452 Int. Cl. A01n 9/36 US. Cl. 424--217 4 Claims ABSTRACT OF THE DISCLOSURE l-Halo-2-aryloxy-vinyl(2) phosphates are very effective compounds for combating pests, such as insects, nematodes and representative of the order Acarina as well as plant-pathogenic bacteria and fungi and may be used in the form of pesticidal preparations.

This is a division of application Ser. No. 64,648 filed on Aug. 17, 1970, now US. Pat. No. 3,732,343.

This invention relates to phosphoric acid esters having pesticidal properties, and to a process for their preparation.

The present invention provides compounds having the formula 0 HC-Hal in which Hal represents a bromine atom or a chlorine atom, R and R which may be the same or different, each represents an alkyl radical having from 1 to 4 carbon atoms and R represents an aryl radical, especially a phenyl or naphthyl radical, which may be substituted by a halogen atom, an alkyl radical having from 1 to 4 carbon atoms, an alkoxy radical having from 1 to 4 carbon atoms, an alkylthio radical having from 1 to 4 carbon atoms, an alkylsulphinyl or alkylsulphonyl radical having from 1 to 4 carbon atoms, NO CF CN, SCN, a COOalkyl radical, the alkyl moiety of which has from 1 to 4 carbon atoms or a --C-Oalkyl radical, the alkyl moiety of which has from 1 to 4 carbon atoms. The term halogen as used herein encompasses fluorine, chlorine, bromine and iodine.

Preferred compounds are those having the formula I, in which Hal represents a chlorine atom or a bromine atom, R and R each represent a methyl or ethyl radical and R represents a phenyl group which may be substituted by one or more of the following substituents:

halogen, methyl, ethyl, methoxy, ethoxy, methylmer capto, methylsulphinyl, methylsulphonyl, NO

CF CN, --SCN, carbethoxy, carbomethoxy, acetyl or propionyl.

The compounds which are especially preferred are those in which Hal represents a chlorine atom and R represents a phenyl group substituted by one or more of the following substituents: chlorine, bromine, iodine, CN, NO or CF and which can additionally also contain a methyl or ethyl group.

The phosphoric acid esters of the formula I are, for example, active against insects, nematodes and representatives of the order Acarina, and also against plantpathogenic bacteria and fungi. When used in appropriately greater amounts, they also show herbicidal and defoliating action.

3,840,660 Patented Oct. 8, 1974 Their main field of use is combatting all stages of development of sucking and biting insects and Acarina, that is to say, of eggs, larvae, pupae, chrysales and adults or imagines.

The sucking insects include Diptera and Hymenoptera, for example, aphids (Aphidae) such a Nyzus persicae, Doralis fabae, Rhopalosiphum paa'i, Macrosiphum pz'si, Macrosiphum solanifolii, Cryptomyzus korschelti, Sappaphis mali, Hyalopterws arundinis and Myzus cerasi, shield lice and woolly lice (Coccina), for example, Asphia'iatus hederae, Lecanium hesperidum Pseudococcus maritimus, and varieties of Thrips (Thysanoptera), for example, Hercz'nothrips femoralis, bugs, for example, Piesma quadrata, Rhondnius prolixus and Triatoma infestans, and cicadas, for example, Euscelis bilobatus or Nephotettix bipunctatus.

Amongst the biting insects, there should be mentioned Lepidoptera and Coleoptera, for example Plutella maculipennis, Lymantria dispar, Euproctis chrysorrhoea, Malocosoma neustria, Mamestra brassicae, Agrotis segetum, Pieris brassicae and Prodenia litura, Ephesita kuhniella, and Galleria mellonella, as well as storage pests, for example, Dermestes frischii, T rogaa'erma granarius, Tribolium castaneum, Calandra and Sitophilus zea mais, Stegobium paniceum, Tenebrz'o molitor, Oryzaephilus surinamensis, Blattela germanica, Periplaneta americana, Blatta orientalis, Blaberus gigantus, Blaberus fuscus, Gryllus domeslicus, Sitophilus granarius and Leptinotarsa decemlineata; varieties which inhabit the soil, for example, Agriotes sp. and Melolontha melontha; and termites, for example, Leucotermes sp. or Leucotermes flavipes.

A substantial number of pests is to be found under the order Acaria, for example mites and amongst these especially spider mites (Tetranychidae) for example Tetranychus telarius, T. althaeae, T. urticae, Paratetranychus pilosus and Panoychus ulmi, and gall mites (Eriophyes ribis) and Tarasonemidae, for example, Hemitarsomenus latus or Tassonemus pallidus.

The order Acarina however also includes the ticks, that is to say, ectoparasites such as Boophilus microplus, Dermanyssus gal-linae, Ornithonyssus bacoti, Ornithonyssus sylviarum Rhipz'cephalus bursa, Penumonyssus canium, Laelaps nutalli, Acarapis woodi and Pacrergates ovis.

This summary of pests does not in any way claim to be complete. Fundamentally, the phosphates of the formula I have a powerful action against insects and Acarina which are known as pests in crop plant cultures. Thus, say, the rice stem borer Chilo suppressalis is completely destroyed by 0.02% of the compounds of the present invention.

Apart from the insecticidal and acaricidal action, the compounds of the formula I also show a powerful action against plant-pathogenic nematodes, of which the following orders may be mentioned:

A phelenchoides, for example, A phelenchust ritzemabosi, Aphelenchus fragariae, and Aphelenchus cryzae, Dithylenchoides, for example Ditylenchus dipsaci, Meloidogyne, for example Meloidogyne arenaria and Meloidogyne incognira, and cyst-forming nematodes (Heterodera), for example, Heteroa'era rostochianis, and Heterodera schachtii, and root nematodes such as Pratylenchus, Paratylenchus, Rotylenchus, Xiphinema and Rahadopholus.

The present invention also provides pesticidal preparations which comprise, as active ingredient, at least one phosphoric acid ester of the formula HC-Hal in which Hal, R R and R have the meanings specified above, together with a suitable carrier, for example, a

solvent, diluent, dispersing agent, emulsifier, adhesive, thickener, or binder and, if desired other pesticides, for example, insecticides, acaricides, nematocides, bactericides and fungicides.

The active ingredients can be used in the most diverse manner, for example, in the form of sprays, concentrates, dusting powders, scattering agents, granules, fly plates or impregnated strips.

In order to manufacture directly sprayable solutions of the compounds of the formula (I) it is for example possible to use mineral oil fractions of high to medium boiling range, such as diesel oil or kerosene, coal tar oil and oil of vegetable or animal origin, as well as hydrocarbons, for example alkylated naphthalenes or tetrahydronaphthalene, optionally using xylene mixtures, cyclohexanols, ketones and also chlorinated hydrocarbons, such as trichlorethane, trichlorethylene or trichlorobenzenes and tetrachlorobenzenes. Advantageously, organic solvents of boiling point above 100 C. are used.

Aqueous application forms are particularly appropriately prepared from emulsion concentrates, pastes or wettable spraying powders by adding water. Possible emulsifiers or dispersing agents are non-ionic products, for example condensation products of aliphatic alcohols, amines or carboxylic acids, having a long-chain hydrocarbon radical of about to carbon atoms, with ethylene oxide, for example the condensation product of octadecyl alcohol and to mols of ethylene oxide, or that of technical oleylamine and 15 mols of ethylene oxide or that of dodecylmercaptan and 12 mols of ethylene oxide. As anionic emulsifiers there may be mentioned: the sodium salt of dodecyl alcohol sulphuric acid ester, the sodium salt of dodecyl benzenesulphonic acid, the potassium or triethanolamine salt of oleic acid or of abietic acid or of mixtures of these acids, or the sodium salt of a petroleumsulphonic acid. Possible cationic dispersing agents are quaternary ammonium compounds, such as cetylpyridium bromide, or dihydroxyethylbenzyldodecylammonium chlo-' ride.

Talc, kaolin, bentonite, calcium carbonate and calcium phosphate, but also charcoal, cork powder, wood flour and other materials of vegetable origin, can be employed for the manufacture of dusting agents and sprinklingagents.

Granules can be manufactured very simply by dissolving an active substance of formula (I) in an organic sol vent and applying the solution thus obtained to a granular mineral, for example attapulgite, SiO granicalcium, bentonite and the like, and then again evaporating the organic solvent.

Polymer granules can also be used. They can be manufactured by mixing the active substances of formula I with polymerisable compounds (urea/formaldehyde, dicyandiamide/formaldehyde, melamine/formaldehyde or others), after which a polymerisation is carried out under mild conditions, which leaves the active substances unaffected, with the granulation being carried out whilst the gel formation is still proceeding. It is more advantageous to impregnate finished porous polymer granules (urea/ formaldehyde, polyacrylonitrile, polyesters or others) having a particular surface and an advantageous predeterminable adsorption/desorption ratio, with the active substances, for example in the form of their solutions (in a low-boiling solvent) and to remove the solvent. Such polymer granules can, in the form of micro-granules of bulk densities of preferably 300 g./litre to 600 g./litre, also be applied with the aid of atomisers. Atomising can be carried out over large areas of crop plant cultures by means of aircraft.

Of course pesticides, fertilisers, surface-active agents or substances for increasing the specific gravity, such as BaSO can be added to the granules.

Granules are also obtainable by compacting the carrier material with the active substances and additives, and subsequent comminution.

The various use forms can, in the usual manner, he provided with additions of substances which improve the 4 distribution, the adhesion, the rain resistance or the penetrating power; fatty acids, resin, glue, casein, or alginates may be mentioned as such substances.

In general, the agents contain between 0.01 and 95 percent by weight of active substance, preferably 0.1 to percent by weight. In certain special fields of use, for example in the case of applications by aircraft, technically pure active substance can also be employed and sprayed.

T o broaden the spectrum of action, the active substances of formula I can be combined with known insecticidal, acaricidal and/or nematocidal active substances, of which the following may for example be mentioned.

PHOSPHORIS ACID DERIVATIVES Bis-0,0-diethylphosphoric acid anhydride (TEPP) 0,0,0, O-Tetrapropyldithiopyrophosphate Dimethyl 2,2, Z-trichlorol-hydroxyethyl) pho sphonate (TRICHRORFON) l,Z-Dibromo-2,Z-dichlorethyldimethylphosphate (NALED) 2,2-Dichlorovinyldimethylphosphate (DICHLORFOS) 2-Methoxycarbamyl-1-methylviny1dimethylphosphate (MEVINPHOS) Dimethyl-1-methyl-2- (methylcarbamoyl) vinylpho sphate cis (MONOCROTOPHOS) 3- (Dimethoxyphosphinyloxy -N-methyl-N-methoxycis-crotonamide 3- (Dimethoxyphosphinyloxy) -N,N-dimethyl-ciscrotonamide (DICROTOPHOS) 2-Chl0ro-2-diethylcarbamoyl- 1 -methylvinyldirnethylphosphate (PHOSPHAMID ON) 0,0-Diethyl-O-2- (ethylthio -ethylthiophosphate (DEMETON) 0,0-diethyl-S-2- (ethylthio) -ethylthiophosphate S-Ethylthioethyl-0,0-dimethyl-dithiophosphate (THIOMETON) O, O-Diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE) 0,0-Diethyl-S-2- (ethylthio ethyl] dithiophosphate (DISULFOTON) 0,0-Dimethyl-S-2- (ethylsulphinyl) ethylthiophosphate (OXYD-EMETONMETI-IYL) 0,0-Dimethyl-S-( 1,2-dicarbethoxyethyl) dithiophosphate (MALATHION (0,0,0,0-Tetraethyl-S,S-methylene-bis- [dithiophosphate] (ETHION) O-Ethyl-S,S-dipropyldithiophosphate 0,0-Dimethyl-S- (N-methyl-N-formylcarbamoylmethyl) -dithiophosphate (FORMOTION) 0,0-Dimethyl-S- (N-methylcarbamoylmethyl) dithiopho sphate (DIMETHAT) O,O-Dimethyl-S- (N-ethylcarbamoylmethyl) dithiopho sph ate (ETHOATMETHYL) 0,0-Diethyl-S- (N-isopropylcarb amoylmethyl) -dithi0- phosphate (PROTHOAT) S-N- 1-Cyan0-1-methylethyl) carb amoylmethyldiethylthiolphosphate (CYANTHOAT) S- (2-Acetamidoethyl -O-,O-dimethyldithio phosphate Hex amethylpho sphoric acid triamide (HEMPA) 0,0-Dimethyl- O-p-nitrophenylthiopho sphate (PARATHION-METHYL) 0,0-Diethyl-O-p-nitrophenylthiopho sphate PARATHION O-Ethyl-O-p-nitrophenylthiophosphonate (EPN) 0,0-Dimethyl-O'- (4-nitro-m-tolyl) thiophosphate (FENITROTHION) 0,0-Dimethyl-O- 2-chloro-4-nitrophenylthiophosphate DICAPTI-ION) 0,0-Dimethyl-O-p-cyanophenylthiopho sphate (CYANOX) O-Ethyl- O-p-cyanophenylphenylthiophosphonate 0,0-Diethyl-0 2,4- dichlorophenylthiophosphate (DICHROFENTHION) 'O-2,4-Dichlorophenyl-O-methylisopropylamidothiophosphate 9 2-Fluoro-N-methyl-N'( l-naphthyl) -a'cetamide Pentachlorophenol and salts 2,2,2-Trichloro-N-(pentachlorophenyl)acetimidoyl chloride N-(4-Chloro-2-methylphenyl)-N,N-dimethylformamidine (Chlorphenamidine) 4-Chlorobenzyl-4-fluorophenyl-sulphide (Fluorobenside) 5,6-Dichloro-1phenoxycarbanyl-Z-trifiuoromethylbenzimidazole (Fenozaflor) Tricyclohexyl-tin hydroxide Z-Thiocyanatoethyl-lauric acid ester fl-Butoxy-p thiocyanatodiethyl-ether Isobornyl-thiocyanatoacetate p-Chlorophenyl-p-chlorobenzenesulphonate (Ovex) 2,4-Dichlorophenyl-benzenesulphonate p-Chlorophenyl-benzenesulphonate (Fenson) p-Chlorophenyl-2,4,S-trichlorophenylsulphone (Tetradifon) p-Chlorophenyl-2,4,S-trichlorophenylsulphide (Tetrasul) Methyl bromide p-Chlorophenyl-phenylsulphone p-Chlorobenzyl-p-chlorophenylsulphide (Chloribenside) 4-Chlorophenyl-2,4,S-trichlorophenylazosulPhide 2-(p-tert.-Butylphenoxy-l-methyl-Z-chloroethyl-sulphite 2(p-tert.-Butylphenoxy) cyclohexylZ-propinyl-sulphite 4,4-Dichloro-N-methylbenzenesulphonanilide N-(2-Fluoro-1,1,2,2-tetrachlorethylthio)-methanesulphonanilide 2-Thio-1,S-dithiolo-(4,5,6)quinoxaline (Thioquinox) Chloromethyl-p-chlorophenylsulphone (lauseto (sic!) new) 1,3,6,8-Tetranitrocarbazole and Prop-2-ynyl-(4-t-butylphenoxy)-cyclohexylsulphite (propargil).

The action of the phosphoric acid esters of the formula I according to the present invention, can be increased by synergistic agents. Suitable substances for this purpose are, for example, Sesamine, Sesamex, piperony'l cyclonene, piperonyl butoxide, piperonal bis [2-(2-bu'toxyethoxy) ethyl] acetate, sulphoxides, propyl isome, N-(2-ethylhexyl)--norbornene-2, 3 dicarboxamide, octachlorodipropyl-ether, 2-nitrophenyl-propargyl-ether, 4 chloro-Z- nitrophenyl-propargyl-ether, and 2,4,5 trichlorophenylpropargyl-ether.

The present invention also provides a process for the manufacture of the phosphoric acid esters of the formula I, which comprises reacting a dihalogenacetic acid ester of the formula in which Hal represents a chlorine atom or a bromine atom and R, has the meaning specified above, with a trialkylphosphite of the formula i R O-I|OR4 in which R and R, have the meanings specified above and 1g represents an alkyl radical having from 1 to 4 carbon atoms. The reaction can be carried out in a solvent, for example, toluene, xylene, petrol ether or dioxane, depending upon the speed or sluggishness of the particular reaction.

This reaction is surprising, since it is expressly stated in the literature (F.W. Lichtenthaler, Chem. Rev. 61, 612 [1961]), in elaboration of the Perkow reaction, that the reaction of triethylphosphite with dichloracetic acid ethyl ester only yields undefined end products together with C I-I Cl. Dichloroacetic acid esters, so it is said, are not suitable for the Perkow reaction.

The following Examples illustrate the invention.

EXAMPLE 1 0,0-diethyl-1- (4-chlorophenoxy)2-chloro-vinylphosphate 0 HC-Cl (Active substance No.1)

47.6 g. of dichloroacetic acid 4-chlorophenyl ester were dissolved in ml. of toluene. 40 g. of triethylphosphite were added to this solution, after which the reaction mixture was warmed to C. and kept at this temperature for 16 hours.

The toluene was subsequently distilled off and the crude product was purified by means of a molecular distillation apparatus.

Yield 35.3 g.; boiling point: 100 C./0.003-0.004 mm. H Analysis for C H Cl O P: Calculated, Percent: P, 9.1; Cl, 20.8. Found, Percent: P, 8.9; C1, 21.3.

The structure of the product was confirmed by means of infrared analysis. On addition of SO CI in CH CI Cl; was added to the double bond. The resulting yellowish 'irichlorethyl phosphate shows the following analytical figures for C H Cl O P: Calculated, Percent: P, 7.52; Cl, 34.42. Found, percent: P, 7.7; Cl, 34.9.

The following phosphoric acid esters can be obtained (Hal) CHCOOR 50 in a similar manner:

. Boiling point/ R1=Rz Hal R: mm. Hg

Active substance number:

2 CzHl Cl 100 C./0.001 l 3.....- C Cl 124 C. 0.005

4 on. C1 0.10.001 I 6 CHI Cl 0.10.001 l I NO:

See footnote at end of table.

TABLE-C0ntinued 1 Boiling point] R1=Rz H al Ra mm. Hg

Active substance number:

43 02H 01 Cl 137 C./0.001

45 02H; 01 (3H, 135 C./0.001 1 46 CzH 01 CH; 136 010.001;

47 02H 01 C./0.001 l 48.. 01H; 01 Q C./0.005 1 I OCH:

50 CQHI Cl C.Cl5 180 C./0.08

51 CH: Cl 125 C./0.001 1 52 CzH G1 145 C./0.005 1 53 CzH| C1 C1 (ll/01001 l 57 CzHu C1 Q 140 C./0.005 1 1 Molecular distillation. I Melting point 90 C. I Cannot be distilled. l Melting point 84 C.

as well as the compounds Boiling point] R1=R2 Hal R: mm. Hg

Active substance umber:

58 O HC-Br Boiling pointm,

II M 142-146" 0. (C2H5O)2POCO C1 59 O BIC-Br Boiling point ll I! 145-149 0. (CzHO)zPOC-0- C1 60 O HC-Br Cannot be distilled. (C2H5O)1PO-C-O NO;

61 O HC-Br Boiling pointom,

I] (I!1 138 0. (C:H)2PO-- O Cl l Cl 62 Same as above Boiling polnt m,

63 O HC-Br Bolling point II 11 140-143 0. (CnH50)2PO-C-0 64 O HC-Br Boiling pointo II II 107l08 0. 2 50)2P-OCO 6" CH: Bolling olnt 0 fl) BIC-Br 151 C? o (C2H50)aP-O-0 Cl 66 CH3 Boiling polntmm,

fl) HC-Br 148-149 0. (CzH5O):POi J-O Cl 67 (H) H fi01 Boiling polntm,

(iso) oin7or *-o-o-o--ci 129 0.

O O H 6% 0 HC 01 Boiling point H II 132 0. 1 (lso)C;H O1!-OC-O Cl 0 OH:

1 Molecular distillation.

EXAMPLE 2 (c) Emulsion concentrate Easily soluble active substances can also be formulated (a) Dusting agents Equal parts of an active substance according to the invention and of precipitated silica are finely ground. Dusting agents preferably containing 1-6% of active substance can be manufactured therefrom by mixing with kaolin or talc.

(b) Spraying powders In order to manufacture a spraying powder, the following components are for example mixed and finely ground:

as an emulsion concentrate according to the following instruction:

20 parts 70 parts of xylene and 10 parts of a. mixture of the reaction product of an alkyl phenol with ethylene oxide and calcium dodecylbenzene sulphon'ate are mixed. On dilution with water to the desired concentration, a sprayable emulsion is produced.

(d) Granules (a) 7.5 g. of one of the active substances of formula I are dissolved in ml. of acetone and the acetone solution thus obtained is added to 92 g. of granular attapulgite (mesh size: 24/48 meshes/ inch). The whole is Well mixed and the solvent is stirpped off in a rotary evaporator. Graidules contamm' g 7.5% of active substance are obtain (b) In order to manufacture 10% strength polymer granules, 1050 to 1100 g. of technical active substance of formula I are dissolved in 2 litres of trichlorethylene and sprayed in a fluidised bed granulators, at 1.5 atmospheres gauge spraying pressure, onto 9230 g. of initially introduced porous urea/HCHO-granules. The solvent can again be removed by heating the fluidising air to approx. 50 C.

(c) In order to manufacture 7.5% strength weighted granules, 770 g. of a solid technical active substance of formula I, 500 g. of BaSO 1000 g. of urea and 7730 g. of pulverulent, porous polyacrylonitrile are pressed on a roll mill and subsequently crushed to the desired particle size.

EXAMPLE 3 Contact action on Musca domestica (L.) and Ceratitis capitata Active Substance N o. 1

Musca Ceratitts domestz'ca capitata Concentration (p.p.m.):

EXAMPLE 4 Action against Spodoplera littoralis larvae 5 larvae at a time, in the L-2 stage, are placed on a leaf of Malva silvestris which originates from a plant dipped into an aqueous solution of an active substance, and which had subsequently been introduced into a covered Petri dish. The atmospheric moisture in the dish is maintained with a moistened pad of cottonwool. In this contact test and ingestion test the action was examined after 1 day and after 2 days. If complete destruction has already occurred after 1 day for a particular concentration, a fresh leaf of the same plant is infested with a new population. In this way a possible ageing of the active substance coating is also taken into account in the assessment.

For active substance No. 25, the following destruction percentages were found:

1 day 2 days Concentration EXAMPLE 5 20 by counting the live and dead animals and by calculating the percentage destruction.

For active substance No. 43 the following percentages of destruction were found:

Concentration, p.p.m. 5 days 800 100 400 100 200 100 100 100 50 100 25 100 2 days 5 days Concentration (p.p.m.):

EXAMPLE 6 Action against Chilo suppressalis (larvae) lACtiVO substances No. 1 and 2 were tested for their ingestion action against L-2 larvae. For this test, the larvae were placed on the root structure of rice seedlings which had previously been treated by dipping in an emulsion of the active substance.

The evaluation took place after 5 days.

Concentration of the active substance in Mortality in percent for active substance the emulsion, p.p.m. No. 1 and No. 2

EXAMPLE 7 Action against Aphis fabae Young Vicia faba plants approx. 6 cm. high were infested with parts of plants attacked by Aphis fabae. After 5 days the starting conditions for the active substance test were present, as a result of the further growth of the plants and appropriately strong multiplication of the aphids. The attacked plants were sprayed with the emulsions of active substance No. 25 from all sides (contact action), or only from above in the direction of the shoot axis (penetration action). In the latter case, the experimental animals sitting on the undersides of the leaves were not struck by the spray jet. If. 100% destruction had already occurred after 2 days, the plants were re-infested.

Active substance No. 25 achieved the following percentages of destruction after 2 and 5 days:

21 EXAMPLE 8 Action against spider mites Busch bean plants (Phaseolus vulgaris) in the 2-leaf stage were infested with spider mites, 12 hours before the treatment with the active substance, by placing attacked pieces of leaf from a culture on them, so that after the end of this time a population in all stages of development was present on the plant. The plants were then sprayed with the emulsified active substance by means of a chromatography atomiser, until a uniform deposit of droplets was produced on the surface of the leaf. The results were assessed after 2 and 7 days; the parts of the plant were inspected under a stereomicroscope in order to calculate the percentages of destruction. The action on eggs was not yet detectable after 2 days with this experimental arrangement, because the embryo development takes 4 days under the particular conditions. If after 2 days there was 100% destruction of larvae and adults, the plant was re-infested.

The percentages of destruction of the normally sensitive variety Tetranychus urticae Koch and of the phosphoric acid ester-tolerant variety Tetranychus telarius L. are given in the Table below.

Active substance N0. 1

(a) Action against Tetr. umcae Destruction after- 2 days 7 days Larvae Adults Eggs Larvae Adults Concentration,

(b) Action against Tetr. telarius Active substance N0.

(a) Action against Tetr. urticae Destruction after 2 days 7 days Larvae Adults Eggs Larvae Adults Concentration,

p.p.m

(b) Action against Tetr. telarius EXAMPLE 9 Action against ectoparasites and vectors Ticks (A) Rhipicephalus bursa (adults). The experimental animals were briefly treated with aqueous solutions of a dilution series of the active substance. Assessment after 2 weeks.

(B) Rhipicephalus bursa (larvae). Method as under (B) Assessment after 3 days.

(C) Boophilus microplus (larvae). Method as under (B) Assessment after 3 days.

Vectors (D) Lucilia sericata (larvae). Chopped horsemeat, mixed with dilution concentrations of an active substance, were administered as food to the larvae of the blow-fly. Assessment after 24 hours.

22 (E) Aedes aegypti (larvae). The larvae of the yellow fever mosquito were kept in a very dilute aqueous solution of active substance. Assessment after 24 hours. Minimum concentrations for complete destruction:

A, B, C, D, E, p.p.m. p.p.m. p.p.m. p.p.m. p.p.m.

Active substance number- EXAMPLE 10 Action against storage pests when using a 5% strength dust formulation based on talc.

EXAMPLE 10 Minimum of active substance for 100% destruction 24 hours exposure time (mg. of active substance per ml), Compound Varieties of test animal No. 37

German cockroach (Phyllodromia germam'ca) 12 American cockroach (Periplaneta americana) 50 Russian cockroach (Blatta orientalis) 50 Flour weevil (Tenebrio molitor):

Imago" 5O Larva... 100 Bacon weevil (Dermestes fnscht mago 50 Larva"... 12 Sitophz'lus granartus (larva) 50 Fur weevil (Attagemts pzceus) larva 50 House cricket (Acheia domestica) 100 EXAMPLE 11 Fungicidal action (1) Rice plants were grown in a greenhouse and sprayed once, prophylactically, with an aqueous spraying liquor containing 0.1% of the active substance No. 21. Two days thereafter, the plants treated in this way were infected with conidia of Piricularia oryzae Bri. and Cav. After 7 days incubation in a humidity chamber, the plants treated with the experimental preparation showed a fungal attack of about 10%, whilst the untreated control plants were 100% attacked.

(2) Small agar plates on which lRhizoctonia solani Kiihn had grown were covered, in Petri dishes, with nonsterile soil. An aqueous liquor containing active substance No. 38 which was to be tested, was uniformly distributed over the surface of these layers of soil. After an incubation time of 48 hours at 24 C. the growth of the test fungus was examined and accessed. Herein, a test concentration of 100 ppm. of active substance showed complete inhibition of fungal growth.

What is claimed is:

1. A method for controlling plant pathogenic fungi which comprises applying thereto a fungicidally effective amount of a compound of the formula in which Hal represents chlorine or bromine; each of R and R represents alkyl of from 1 to 4 carbon atoms; and R represents phenyl, naphthyl or phenyl substituted by from 1 to 5 substituents selected from the group consisting of chlorine, bromine, iodine, alkyl of from 1 to 4 carbon atoms, alkoxy of from 1 to 4 carbon atoms, alkylthio of from 1 to 4 carbon atoms, nitro, trifiuorornethyl, cyano, the group -COO-alkyl in which the alkyl group has from 1 to 4 carbon atoms and the group --CO-alkyl in which the alkyl has from 1 to 4 carbon atoms.

2. The method of Claim 1 in which, in the compound, each of R and R represents methyl or ethyl; and R References Cited UNITED STATES PATENTS 2,861,914 11/1958 Callmann 260-951 XR 3,732,343 5/1973 Martin et al. 260951 ALBERT T. MEYERS, Primary Examiner L. SCHENKMAN, Assistant Examiner US. Cl. X.R. 

1. A METHOD FOR CONTROLLING PLANT PATHOGENIC FUNGI WHICH COMPRISES APPLYING THEREOT A FUNGICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA 